Hydrocarbon derivative



' pedienjcy, hereinafter reference w I I more particularly to the alkyl chloride and their HYDRQCARBON DERIVATIVE Frederick E. Frey, Bartlesville, kla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application March 28, 1939, Serial N0. 264,650

19 Claims.

This invention relates to improvements in the production of derivatives of parafiln hydrocarbons. It relates especially to derivatives of parafiln hydrocarbons containing a quaternary carbon atom, that is, with the structure'CRA, where B may be any alkyl group, and more specifically to derivatives of these compounds in which at least one of the Rs is a methyl group.

An object of my invention is to produce parafin halides and dihalid'es wherein the halogen is held by a carbon atom directly attached to a quaternary carbon atom, which are designated neoparaflin halideshereafter.

A further object is the production of alcohols and esters, such as acetates, with the hydroxyl group or ester linkage attached to a carbon atom directly attached to a'quaternary carbon atom.

A still further object is the preparation of olefins containing the group CR3, and derivatives of such olefins.

Still another object is the production of large quantities of neoalkyl chlorides, and the like, of a v high degree of purity without expensive and compounds are not only extensively used as such,

but they' are also intermediate compounds in the formation of alcohols, esters, others and other such compounds from hydrocarbons. Of the, alkyl halides used, the alkyl chlorides, or chloroparaffins, have found the largest and widest in- However, the other alkyl halides are similar in their. chemical characteristics, although their physical characteristics such as their boiling points often difier widely, and they may be pre pared in analogous manners. For the sake of exformation and chemical reactions, but it is understood that the other halides and halogehs are not=to be disregarded, and are included in the broadest conceptions of this invention.

Any-number of hydrogen: atoms in a hydrocar bon maybe substitutedfor by a halogen, such as by chlorine. With a few exceptions, however, it

be made are of greatest interest, and it is with these that my invention is concerned. Considering the monosubstituted halogens, it is well known that, in any series of compounds such as the alkyl chlorides, there are three types. Althou h many characteristics ofsuch a series are common to all three types, each type has characteristics which serve to diiierentlate it from the others. These three types are (1) primary, (2) secondary and (3) tertiary compounds, in which the halogen is directly attached to a carbon atom which in turn is directly attached to one, two and three other carbon atoms, respectively. Of these various types of halides the primary alkyl halides are generally considered most desirable, for reasons which need not be elaborated here, while the secondary and tertiary compounds are considered less desirable. Thus, not only are primary alkyl halides more stable during use, but derivatives such as alcohols and esters are the least readily decomposed while they are in use.

There are a number of paraflin hydrocarbons from which only primary halides, can be formed. Among these may be listed such parafllns as, methane (CH4), ethane (CzHs), neopentane ((CH3)4C) 'and neooctane ((CHs)aCC(CI-Is)a). From other parafflns, such as isopentane ((CH:)2CC1CH2CH:), and it has beenwell established that, in any method of producing one of these directly by the chlorination of lsopentane,

large proportions of the others are also produced. The chemical and physical properties of these compounds are such that they are not readily separated, one from the other, and it is difilcult to isolate large quantities of either of the two monochlorides in a pure state.

' is has previously been stated, the primary monochlorides find a larger and wider commeris the mono'and disubstituted paraifins which v cial application. I have found that the neoalkyl halides, that is the primary halides in' which the halogen is attached to a carbon atom which in turn is one of four carbon atoms attached to still another carbon atom such as neopentyl chloride (CHzClC (CH3) 3) neohexyl chloride (CH2C1(CH3) 2CCH2CH3) isoneoheptyl chloride (CH2C1(CH3) 2CCH(CH3) a) 2 n-neoheptyl chloride (omcucmmwmmm and the like appear to be unique amongthemselves, of the primary halides, and are extremely stable and resistant to hydrolysis anddecompositaining more halogen atoms may be formed at the same time under thepreferred operating conditions discussed they are formed only in small amounts, and they generally have a considerably tion. It will be noted that allof these compounds 5 higher boiling point and canbe separated readily carbon. that is, theyfall have the formula M, where x is a halogen, inthis casechlorine'. and R has alkyl group. I

Although only one monochloride is possible upon the chlorination oi neopentane,-there are a number of monochlorides possible from the chlorination of neohexane, isoneoheptane, n-neofrom the resulting mixture by, distillation. These various isomeric monohalides are not widely dif-- ferent in boiling points. and there has not been proposed any method by which the neoalkyl halides may be separated from their isomers and other alkyl halides of adjacent boiling points.

I am now ableto accomplish such a separation and purification by subjecting a mixture containing neoalkyl halides and other halides to elevated heptane and the like. The various monochlo is te pe tu s o a limited period of time. I prerides possible from any one such paramn have boiling points quite close to each other and to other compounds which might be. present as impurities. Fractional distillation is one of the fer to do this in the presence of a catalyst alh p though this is not necessary in every case. Temperatures which I may use are generally above about 175' (3., but I prefer not to use temperamost economical and generally used methods of m tures in excess of about 700' C. The pr ssur separation, but is often difficult or impracticable due to the presence of'overlapping distilling tem- K peratures among the isomeric chlorides obtained from a chlorination step.

- I have now found a novel process for preparing...

process I first treat a neoparaflln in-a pure or m relatively concentrated form with a halogensuch 'as chlorine. Although the neoparaiilns are not naturally plentiful or tube found in concentrated form, they may be prepared in such a form, or

may be in the neighborhood of atmospheric or higher. As catalysts I may employ natural earths such as bauxite and kaolin, metallic oxides such as alumina, thoria and sirconia, and salts such as barium chloride, calcium chloride, calcium phosphate and ferric chloride and the like, either alone or deposited on various supp rts such as silica gel, pumice, charcoal and the like-or in fact any of the catalytic substances which are capable of eilecting elision of KCl between two adjacent carbon atoms, one carrying hydrogen and the other halogen. I have found that catalysts capable of effecting elision of hydrogen chloride between two adjacent carbon atoms and selected from isolated in a high degree of purity. y the process oxides of metals of the third and fourth groups such as is described in the copending application ,of l 'reyand Hepp, Serial Number 108,482, filed I and of the halidesof the calcium subgroup of .the second group 0 the periodic table can be particularly eil tive for use as catalysts in the presence of my invention. when using carried outb'y methods knowntothe-art.suchas s h ca l ts. I am generally able to 9- thermal reaction. or in the presence of catalysts, or under-the influence of actinic light. In any case; the halogen reacts with the paraflin by substitution, substituting forum or more hydrogen vf atoms in the molecule,'the hydrogen so substituted forming hydrogen halide. The neoparai'iin is preferably present in large excess, relative to halogen. and the use of high temperatures up to about 700' C. and either low pressures or high crate successfully in the lower part of the indicated temperature range, vsuch as between pre sure; up t 2,000 pounds per square inch go chloride, is split out from the alkyl halideswhich more with short reaction times of the order of a fraction of a second up to about seconds are suitable, with operation in the lower part of this range being preferred. Under these conditions the formation of polyhalides is restricted, and

' ((CHshCCI-ICICHs) and the desired neohexylchloride (omcucmnccrhcm) and a primary heptyl chloride with the formula (CH3)3CCH(CH:)CH2C1 may be prepared by the chlorination of isoneoheptane as well as the tertiary chlorideand the desired isoneoheptylare present in such a mixture, with the exception of the n'eoalkylha'ides; unafl'ected under. the conditions of operation, and can be recovered in a relatively pure form,depending only upon the degree of purity desired. The other alkyl halides, from which hydrogen halide is split out, are thus transformed into oleflns of the same number of carbon atoms. These oleflns generally have a highly branched charo0 acter, and may bequite valuable compounds themselves, so that my invention may be practiced to form such olefins as well. Thus, from neohexane I may produce an olefin of the formula '(C'Hh) aC-CH=CH:, from isoneoheptane an ole- 05 in of the formula (CH3) :iC-C(CH:)=CH:, etc.

Not only does the practice of my invention produce the neoalkyl halides in a pure state free of I those isomeric alkyl halides resulting from the halogenation of the same paraffin. but in the same 1 7 manner I am able to remove the halides which may have been produced from closely related hydrocarbons. Thus, if it should so happen that some normal hexane, or other isohexanes, are present in crude neohexane or a neohexane conchloride. While other substitution products con-' centrate, these would also be halogenated in any The neoalkylhalides are taining neoalnl halides in accordance with disclosure, the olenns' and hydrogen halide so produced are easily sepatatedirom the remaining alkyl halide. This may be done by simple distillation since the boiling point of the alkyl halide is so much higher, than these other constituents. I! desired the hydrogen halide may be removed by means oi a caustic wash or other equivalent chemical means.

As an example of the operation oi my process neohexane (QJ-dimethylbutane) can be reacted with chlorine by separately heating them both to a temperature oi about 450 0., intimately mixing them and shock cooling the resultant ture alter a reaction period oi'about'l seconds. This is conveniently done with an excess of neoheaane which inhibits over-reaction and the may be treated 'inaccordance. with my invention. iorming CBsC1(OHs)sC(CH:)sCHs and cmciwmwwimn .rupectively and various heptylencs. but the yields oi the desired neoalkylchlorides will be only about 38 percent and ,26 per cent resp ctively the'neoheptanes reacted.

' The term "neoalkylhalide" is used herein to designate the primary halogen substitution prodnote .0! those paraiilns which have'the stmcnire CHsCRr, where R is any alkyl group. such as methyl, ethyl, normal propyl, isopropyl and the like. and-where the substitution has taken place on the methyl group indicated, that is, compounds of the general formula cmxcm. where x u a halogen atom. Although quite high molecular weight compounds may have this structure, high yields of desirable products in a substantially pure state are diillcult to obtain where any of the alkyl groups represented by R has more than four carbon atoms. It is further preierable,.al.- though not absolutely necessary. that one or two oi the allyl groups represented by R be methyl formation oi polyohlorldes. Such an excess is represented by a molar ratio oi hydrocarbon to chlorine or about 8:1 although higher excesses groups, that is. that the paraflins originally treated have the general formula (CHslsCRa 01".: (CHahCR. alkyl halides which do come. within" the, classification o "neoal'bl halides" as xemnccmcmx, normal hexyl "halides. like "are removed zmm fll! neo- -;alkylhalldes bymy process. lmrthermore; a neoalkyl halide or neoparamn monohalide oithe type CHsX(CH:)CRs which haabeen-iorrheda'ndpuriiled as disclosed may be subjected to iurther halogenation, so\ that compound may be obtai another halogen atom will enter into the.mole" cule, forming neoparaflln dih'alides oithe type (CHaCllaORe. along with other halides, and this nedin luminum; pure form by a catalytic treatmentdor elison oi'hydrogen halide exactly similar to that disclosed ior the purification oi the neoalkyl monohalides. Dihalidesot the type'CHClsCRa may .are often used. The three possible monochlorides produced are present in about the ratio given in 7 Table I. r m 1 A. CHaCKCH's) B- 8 V O. (CEfisCGiiCl 36 A fraction boiling between and (2.

containing these three hercylmonochlorides is easily separated iromthe total eiiiuentsq and a fraction representing unre'acted neohexane is returned to be mixed with'i'resh hydrocarbon ooming to the process. The monochloride fraction is then passed over a catalyst comprised oi calcium chloride at a temperature oi about 250 C. The efliuents contain practically all the neoheayl chloride (C'HsCHCHslsCCHaCHs) which been unaiiected, and somewhat smaller amounts of cmnccn==cm. which has been iormed from also be iormed, but under halogenation conditions pointed out as being preferable; such com- .pounds'are formed -only in minor-amoimt's. u I The purined l halides and neoparamn dihalides which are produced in a pure state by my process may be used as such, or they may be converted into alcohols, ethers. esters and the like, by means well known for such conversions.

wThe. derivatives thus formed are also essentially in a pure state, and have properties which ren- 'compoundsBandCoiTableI,asweliaslarge amounts of HCl. Because of the widediiierence in boiling points between the 'neohexyichloride and the neohexylene (boiling point 41.2 C these e'dluents are readily separatedrin commercially pure fractions. The 801 may be removed by fractionation. or by a osusticjwash before or aiter the distillation just mentioned.

In a similar manner isoneoheptylchloride (CH:Cl(CHs):C-CH(CH3)2) is prepared in a commenaally pure state ircm isoneoheptane ((CHs)sC-C H(CHJ)2). when isoneoheptane is chlorinated isoneoheptylchloride is about 50 per cent of the total heptylmonochlorides tomes;

that is, the yield is slightly less than the yields! neohexylchloride. In the same manner the other two heptanes containing quaternary carbon atom. (CHa)sC(OI-Is):CHs and (CHa)2C(CsHs)z ,der them superior over isomeric compound 0! the same molecular weight as the neoalkyi halides are superior over-isomeric alkyi halides.

I claim:

l. A, process for producing der vatives of paraiiin hydrocarbons which comprises treating aparaiiin oi the type'CHsCRs. where each it is any alkyl group oi not more than four carbon atoms; with an elementary halogen whereby a "substitution of halogen ior hydrogen takes place forming isomeric alkyl halides, treating said alkyl halides so vtor-med at a temperatin'e between and 700' C. for a period oi time such that oleiins and hydrogen halide are formed and alkyl halides o! the type CHzXCRa, wherein X lsa halogen, are relatively unaflected, and separat-' ing from the products of said treatment said olelins and hydrogen halide so produced.

3.1:: a process for producing derivatives of paramn hydrocarbons wherein parailln hydro- 1 carbons are treated by halogens producing haloigen substitution products, the steps which corn- 1 v prise treating a hydrocarbon material compris-' ing essentially a parafiin of the group CHaCRa, where each R is any alkyl group of not more than four carbon atoms, with an elementary halogen whereby a substitution of halogen for hydrogen takes place forming alkyl halides treating at least a portion of the halides so formed at a temperature of 175 to 500 C. in the presence of a catalyst for a period of time such that alkyl halides of the type CHzXCRs where X is a halogen, are relatively unaffected and other alkyl halides are decomposed forming olefins and a hydrogen halide, and separating from the products of the treatment the olefins and hydrogen halide so produced.

3. A process for preparing neopentyl chloride in a relatively pure state which comprises treating a parafiinic hydrocarbon material of a narrow boiling range and comprising predominantly neopentane with elementary chlorine under such conditions that alkyl monochlorides are formed, treating at least a portion of said alkyl monochlorides at a temperature between 175 and 700 C. for a period of time such that neopentylchloride is substantially unafi'ected and other alkyl chlorides are decomposed forming olefins and hydrogen chloride, and separating from the products of said treatment the said olefins and hydrogen chloride so produced. a

4. A process for preparing neoheptyl chloride in a relatively pure state which comprises treating a hydrocarbon material comprising essentially neoheptanes with elementary chlorine under such conditions that alkyl monochlorides are formed, treating at least a portion of said alkyl monochlorides at a temperature between 175 and 700 C. for a period of time such that neoheptylchlorides of the group CH2CICR3. where R is an alkyl group, is substantially unaffected and other alkyl chlorides are decomposed forming olefins and hydrogen chloride, and separating from the products of said treatment the said olefins and hydrogen chloride so produced.

5. In a process for producing derivatives of parafiin hydrocarbons in which a parafiln of the type CH3CR3, where each R is any alkyl group of not more than four carbon atoms, is treated with an elementary halogen to form isomeric alkyl halides by substitution of halogen for hydrogen, the improvement which comprises treating said alkyl halides so formed at a temperature between 175 and 700 C. for a period of time such that olefins and hydrogen halide are formed and alkyl halides of the type CHzXCRa, wherein X is a halogen, are relatively unaffected, and separating from the products of said treatment said olefins and hydrogen halide so produced.

6. The process as set forth in claim 5 wherein the halogen is chlorine.

7. In a process for producing derivatives of parafiln hydrocarbons wherein parafiin hydrocarbons are treated by an elementary halogen to produce halogen substitution products, the steps which comprise treating a parailinic hydrocarbon material of a narrow boiling range and comprising predominantly a paraifin of the type CHaCRs, where each R. is any alkyl group of not more than four carbon atoms, with an elementary halogen to form alkyl halides by the substitution of halogen for hydrogen, treating at least a portion of the halides so formed at a temperature between 175-700? (3., for a period of time such that alkyl halides of the type CHZXCRB, wherein X is a halogen, are relatively unaffected such that olefins and hydrogen halide are formed. from ordinary alkyl halides, and separating from the products of said treatment the said olefins and hydrogen halide so produced.

8. The process according to claim 7 wherein the halogen is chlorine.

9. In a process for obtaining an alkyl halide of the type CHzXCRa wherein X is a halogen and each R is any alkyl group of not more than four carbon atoms, in a relatively pure state, the steps which comprise treating a paraffinic hydrocarbon material of a narrow boiling range and comprising predominantly a paraffin of the group CHsCRs with an elementary halogen to form alkyl halides by the substitution of halogen for hydrogen, treating the alkyl halides so formed at a temperature between and 700 C. for a period of time such that the alkyl halides of the group CHzXCRa are relatively unaffected and such that other alkyl halides are decomposed to form olefins and hyrogen halide, and separating from the products of said treatment the said ole fins and hydrogen halide so produced.

10. A process according to claim 9 wherein the halogen is chlorine.

11. In a process for producing derivatives of paraifin hydrocarbons wherein paraffin hyrocarbons are treated by halogens producing halogen substitution products, the steps which comprise treating a paraflinic hydrocarbon material of a narrow boiling range and comprising predominantly a parffin of the type CHsCRa Where each R is any alkyl group of not more than four carbon atoms, with an elementary halogen to form alkyl halides by substitution of halogen for hydrogen, treating at least a portion of the alkyl halides so formed at a temperature between 175 and 500 C. in the presence of a solid catalytic substance capable of eifecting elison of hydrogen chloride between two adjacent carbon atoms, for a period of time such that alkyl halides of the group CHzXCRa are relatively unaffected and such that other alkyl halides are decomposed to form olefins and hydrogen halide, and separating from the products of the treatment the olefins and hydrogen halide so produced.

12. The process according to claim 11 in which the halogen is chlorine.

13. A process for preparing neohexyl chloride in a relatively pure state which comprises treating a parafiinic hydrocarbon material of a narrow boiling range and comprising predominantly neohexane with elementary chlorine under such conditions that alkyl monochlorides are formed,

treating at least a portion of said alkyl monochlorides at a temperature between 175 and 700 C. for a period of time such that the neohexyl chloride CH2C1(CH:)2CCH2CH3 is substantially unaffected and other alkyl chlorides are decomposed forming olefins and hydrogen chloride, and separating from the products of said treatment the said olefins and hyrogen chloride so produced.

14. A process for producing derivatives of parafiin hydrocarbons, which comprises treating a parafiinic hydrocarbon material of a narrow boiling range and comprising predominantly a neoparafiin of the type CHaCRa, where each R is any alkyl group of not more than four carbon atoms, with chlorine to form alkyl chlorides by substitution of chlorine for hydrogen, treating at least a portion of the alkyl chlorides so formed at a temperature and for a period of time adapted to decompose other alkyl chlorides present forming olefins and hydrogen chloride and to leave unaffected alkyl chlorides present of the group CH2C1CR3, and separating from the effluent v prising a neoalkyl oi said treatment oleflns and hydrosen chloride so produced.

15. In a process tor producing derivatives of paraflin hydrocarbons, the improvement which comprises treating an alkyl halide mixture com halide of the type CHsXCRa, where each R is any four carbon atoms and where X is a halogen, along with other-alkyl halides or approximately the same boiling point at a temperature between 175 and 500 C. for a period oi. time adapted to eflect a decomposition oi' said other alkyl halides into oleflns and hydrogen halide and to leave substantially. unaflected said neoalkyl halide, and separatingfrom the eiiiuent of said treatmentoleflns and hydrogen halide s0 produced.

16. A process for preparing a neoalkyl monohalide in arelatively pure state. which comprises treating a paramnic hydrocarbon material of a narrow boiling range and which comprises essentially a neoparai'iin oi! the type (CI-Is} :CR, where Ris any alkyl group oi aliwl group of not more than aerosols monohalides at a temperature time such that said hexyl not more than (our carbon atoms, with elementary chlorine to form alkyl Q chlorides, treating alkyl chlorides so formed at a temperature between 1'76 and 500 C. for a period of time adapted to effect a decomposition 0! other sllwl chlorides forming oleflns and hydrogen chloride, and to leave-substantially unaffected alkyl chlorides oi the group CI-IzCHCHshCR, and separating from the diluent of the treatment oleflns and hydrogen chloride soproduced;

17. In a process for producing derivatives, paraiiln hydrocarbons, .the improvement which comprises treating an alkyl chloride mixture,oomprising a neoalkyl chloride of the type CHzClCR-a,

- .prisinz the where each R is any alkyl group of not'more than tour carbon atoms, along with at least one other alkyl chloride of the same molecular weight andhaving a hydrogen atom and a chlorine atom on v ride into an oieiln adiacent carbon-atoms, at a temn rature between 175 and 500' C. ior aperiod of time suiiicient to eflect a decompos tion unaffected said neoalkyl chloleavesuhstantially from the eflinent of said ride, and separatina treatment olefin duced. g 18. A process for producing a hexyl halide oi the type CI-IsX(CH:)aCC:I-Is, where x is a halo- 8 the said olefin and hydrogen comprises treating an alkyl'clfloride-mixture, com.

hez'yl chloride ,CHsCNCHa) aCCaHI along-with at least one other hexyl chloride, at a temperature between 175 and 500 C. tor a period of time sufllcient to sheet a decomposition 01 said other hexyl chloride into an oleiin and hydrozen chloride and toleave said CHsCKCHDsCCsHa substantially unaiiected, and separating from the" eiiiuent or said treatment olefin and hydroaen chloride so produced.

. i FREDERICKELFREY.

01' said other aikyl chlo= and hydroaen chloride and to and hydrogen chloride soproin a relatively puretstate, which comprises I treating a paramnichydrocarbon material 0! a and-separating from the products y (or producing derivatives of paraiilin hydrocarbons.'-the im rovement which 

